Solar Cell With Selectively Doped Conductive Oxide Layer And Method Of Making The Same

ABSTRACT

A method of making a coated substrate having a transparent conductive oxide layer with a dopant selectively distributed in the layer includes selectively supplying an oxide precursor material and a dopant precursor material to each coating cell of a multi-cell chemical vapor deposition coater, wherein the amount of dopant material supplied is selected to vary the dopant content versus coating depth in the resultant coating.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application No.61/777,316, filed Mar. 12, 2013, herein incorporated by reference in itsentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to solar cells, e.g., photovoltaic (PV)cells, and, more particularly, to a solar cell having a selectivelydoped transparent conductive oxide layer and a method of making thesame.

2. Technical Considerations

A solar cell or photovoltaic (PV) cell is an electronic device thatdirectly converts sunlight into electricity. Light shining on the solarcell produces both a current and a voltage to generate electric power.In a solar cell, photons from sunlight hit the solar cell and areadsorbed by a semiconducting material. Electrons are knocked loose fromtheir atoms, causing an electric potential difference. Current flowsthrough the material to cancel the potential difference. Due to thespecial composition of solar cells, the electrons are only allowed tomove in a single direction.

A conventional amorphous silicon thin film solar cell typically includesa glass substrate (cover plate) over which is provided an underlayer, atransparent conductive oxide (TCO) contact layer, and an amorphoussilicon thin film active layer having a p-n junction. A rear metalliclayer acts as a reflector and back contact. The TCO layer preferably hasan irregular surface to increase light scattering. In solar cells, lightscattering or “haze” is used to trap light in the active region of thecell. The more light that is trapped in the cell, the higher theefficiency that can be obtained. However, the haze cannot be so great asto adversely impact upon the transparency of light through the TCOlayer. Therefore, light trapping is an important issue when trying toimprove the efficiency of solar cells and is particularly important inthin film cell design. It is also desirable if the TCO layer is highlytransparent to permit the maximum amount of solar radiation to pass tothe silicon layer. As a general rule, the more photons that arrive atthe semiconductor material, the higher the efficiency of the cell.Further, the TCO layer should be highly conductive to allow the easytransfer of electrons in the cell. This conductivity can be enhanced bythe addition of a dopant material to the TCO material.

The TCO layer is an important factor in solar cell performance. The TCOmaterial should preferably have a high conductivity (i.e., low sheetresistance), a high transparency in the desired region of theelectromagnetic spectrum, and should have high haze to promote lightscattering. However, these factors are interwoven with each other. Forexample, conductivity is dependant upon the dopant concentration and thethickness of the TCO layer. However, increasing the dopant concentrationor the thickness of the TCO layer generally decreases the transparencyof the TCO layer. Further, surface roughness (light scattering)generally increases with coating thickness. However, increasing thecoating thickness generally decreases the transmission (particularlyvisible light transmission) through the coating. Thus, the affect andinteraction of each of these factors must be weighed when selecting aTCO layer for a solar cell.

It would be desirable to provide a TCO layer in which the conductivity,light transmission, and light scattering could more easily be selected.It would also be desirable to provide a method of providing a TCO layerfor a solar cell in which these factors could be controlled more easily.It would also be desirable to provide a solar cell having such a TCOlayer.

SUMMARY OF THE INVENTION

A solar cell comprises a first substrate having a first surface and asecond surface. A first conductive layer is provided over at least aportion of the second surface, wherein the first conductive layercomprises a transparent conductive oxide layer incorporating a dopantmaterial. The dopant material is selectively distributed in theconductive layer. A semiconductor layer is provided over the transparentfirst conductive layer. A second conductive layer is provided over atleast a portion of the semiconductor layer.

A method of making a coated substrate having a transparent conductiveoxide layer with a dopant selectively distributed in the layer comprisesselectively supplying an oxide precursor material and a dopant precursormaterial to each coating cell of a multi-cell chemical vapor depositioncoater, wherein the amount of dopant material supplied is selected tovary the dopant content versus coating depth in the resultant coating.

A chemical vapor deposition system comprises at least one coater havinga plurality of coating cells, wherein the coating cells are connected toone or more coating supply sources comprising at least one oxideprecursor material and at least one dopant material. In a preferredembodiment, the coating cells are individually connected to respectivecoating supply sources comprising at least one oxide precursor materialand at least one dopant material.

A method of making a coated substrate having a coating layer with adopant selectively distributed in the coating layer comprises: supplyinga coating precursor material to coating cells of a multi-cell chemicalvapor deposition coater; supplying a dopant precursor material tocoating cells of a multi-cell chemical vapor deposition coater;controlling the supply of at least one of the coating precursor materialand the dopant precursor material to define a coating composition havinga selected ratio of the dopant precursor material to the coatingprecursor material at the coating cells; and depositing the coatingcomposition onto a substrate to form a doped coating layer. The ratio ofthe dopant precursor material to the coating precursor material isselected to define a desired dopant content versus coating depth profileof a resultant doped coating.

At least a portion of the coating cells can be individually connected toa coating precursor supply and a dopant precursor supply.

BRIEF DESCRIPTION OF THE DRAWINGS

A complete understanding of the invention will be obtained from thefollowing description when taken in connection with the accompanyingdrawing figures.

FIG. 1 is a side, sectional view (not to scale) of a solar cellincorporating features of the invention;

FIG. 2 is a side, prospective view of a chemical vapor deposition (CVD)coating system (not to scale) incorporating features of the invention;

FIG. 3 is a graph of TFA flow (lb/hr) versus cell number for Example 1;

FIG. 4 is a graph of F/Sn ratio versus coating depth for Example 1;

FIG. 5 is a graph of TFA flow (lb/hr) versus cell number for Example 2;

FIG. 6 is a graph of F/Sn ratio versus coating depth for Example 2;

FIG. 7 is a graph of TFA flow (lb/hr) versus cell number for Example 3;

FIG. 8 is a graph of F/Sn ratio versus coating depth for Example 3;

FIG. 9 is a graph of TFA flow (lb/hr) versus cell number for Example 4;

FIG. 10 is a graph of F/Sn ratio versus coating depth for Example 4;

FIG. 11 is a graph of fluorine and tin content versus coating depth forExample 5;

FIG. 12 is a graph of F/Sn ratio versus coating depth for Example 5;

FIG. 13 is a graph of tin, oxygen, and fluorine content versus coatingdepth for Sample 1 of Example 6;

FIG. 14 is a graph of tin, oxygen, and fluorine content versus coatingdepth for Sample 2 of Example 6;

FIG. 15 is a graph of tin, oxygen, and fluorine content versus coatingdepth for Sample 3 of Example 6;

FIG. 16 is a graph of percent haze versus coating thickness for Example6;

FIG. 17 is a graph of sheet resistance versus coating thickness forExample 6

FIG. 18 is a graph of haze versus wavelength for Example 6.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, spatial or directional terms, such as “left”, “right”,“inner”, “outer”, “above”, “below”, and the like, relate to theinvention as it is shown in the drawing figures. However, it is to beunderstood that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting. Further, as used herein, all numbers expressing dimensions,physical characteristics, processing parameters, quantities ofingredients, reaction conditions, and the like, used in thespecification and claims are to be understood as being modified in allinstances by the term “about”. Accordingly, unless indicated to thecontrary, the numerical values set forth in the following specificationand claims may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical value should at least be construedin light of the number of reported significant digits and by applyingordinary rounding techniques. Moreover, all ranges disclosed herein areto be understood to encompass the beginning and ending range values andany and all subranges subsumed therein. For example, a stated range of“1 to 10” should be considered to include any and all subranges between(and inclusive of) the minimum value of 1 and the maximum value of 10;that is, all subranges beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5,5.5 to 10, and the like. Further, as used herein, the terms “formedover”, “deposited over”, “provided over”, or “located over” mean formed,deposited, provided, or located on a surface but not necessarily indirect contact with the surface. For example, a coating layer “formedover” a substrate does not preclude the presence of one or more othercoating layers or films of the same or different composition locatedbetween the formed coating layer and the substrate. As used herein, theterms “polymer” or “polymeric” include oligomers, homopolymers,copolymers, and terpolymers, e.g., polymers formed from two or moretypes of monomers or polymers. The terms “visible region” or “visiblelight” refer to electromagnetic radiation having a wavelength in therange of 380 nm to 760 nm. The terms “infrared region” or “infraredradiation” refer to electromagnetic radiation having a wavelength in therange of greater than 760 nm to 100,000 nm. The terms “ultravioletregion” or “ultraviolet radiation” mean electromagnetic energy having awavelength in the range of 200 nm to less than 380 nm. The terms“microwave region” or “microwave radiation” refer to electromagneticradiation having a frequency in the range of 300 megahertz to 300gigahertz. Additionally, all documents, such as, but not limited to,issued patents and patent applications, referred to herein are to beconsidered to be “incorporated by reference” in their entirety. In thefollowing discussion, the refractive index values are those for areference wavelength of 550 nanometers (nm). The term “film” refers to aregion of a coating having a desired or selected composition. A “layer”comprises one or more “films”. A “coating” or “coating stack” iscomprised of one or more “layers”.

Although the invention will be described with respect to use with asolar cell, it is to be understood that the invention is not limited touse with solar cells but could be used in other applications, such asarchitectural glazings, organic light-emitting diodes, or solar controltransparencies.

An exemplary solar cell 10 incorporating features of the invention isshown in FIG. 1. The solar cell 10 includes a first (outer) substrate 12having a first (outer) major surface 14 and a second (inner) majorsurface 16. By “outer” is meant the surface facing the incidentradiation, e.g., sunlight. An optional undercoating 18 may be locatedover the second surface 16. A first conductive layer 20 (for example aTCO layer) is located over the second surface 16 (such as on theundercoating 18, if present). A semiconductor layer 22 is located overthe TCO layer 20. A second conductive layer 24 is located over thesemiconductor layer 22. For example, the second conductive layer 24 canbe a metal layer or a metal-containing layer. An optional second (inner)substrate 26 is located over the second conductive layer 24.

In the broad practice of the invention, the first substrate 12 (andoptional second substrate 26, if present) can include any desiredmaterial having any desired characteristics. For example, the firstsubstrate 12 can be transparent or translucent to visible light. By“transparent” is meant having a visible light transmittance of greaterthan 0% up to 100%. Alternatively, the first substrate 12 can betranslucent. By “translucent” is meant allowing electromagnetic energy(e.g., visible light) to pass through but diffusing this energy suchthat objects on the side opposite the viewer are not clearly visible.Examples of suitable materials include, but are not limited to, plasticsubstrates (such as acrylic polymers, such as polyacrylates;polyalkylmethacrylates, such as polymethylmethacrylates,polyethylmethacrylates, polypropylmethacrylates, and the like;polyurethanes; polycarbonates; polyalkylterephthalates, such aspolyethyleneterephthalate (PET), polypropyleneterephthalates,polybutyleneterephthalates, and the like; polysiloxane-containingpolymers; or copolymers of any monomers for preparing these, or anymixtures thereof); glass substrates; or mixtures or combinations of anyof the above. For example, the first substrate 12 can includeconventional soda-lime-silicate glass, borosilicate glass, or leadedglass. The glass can be clear glass. By “clear glass” is meantnon-tinted or non-colored glass. Alternatively, the glass can be tintedor otherwise colored glass. The glass can be annealed or heat-treatedglass. As used herein, the term “heat treated” means tempered or atleast partially tempered. The glass can be of any type, such asconventional float glass, and can be of any composition having anyoptical properties, e.g., any value of visible transmission, ultraviolettransmission, infrared transmission, and/or total solar energytransmission. By “float glass” is meant glass formed by a conventionalfloat process in which molten glass is deposited onto a molten metalbath, such as molten tin. The bottom side of the glass, i.e., the sidethat was in contact with the molten tin bath, conventionally is referredto as the “tin side” and the top side of the glass conventionally isreferred to as the “air side”. The tin side of the glass can have smallamounts of tin incorporated into the glass surface. Non-limitingexamples of glass that can be used for the practice of the inventioninclude Solargreen®, Solextra®, GL-20®, GL-35™, Solarbronze®,Starphire®, Solarphire®, Solarphire PV® and Solargray® glass, allcommercially available from PPG Industries Inc. of Pittsburgh, Pa.

The first substrate 12 can be of any desired dimensions, e.g., length,width, shape, or thickness. For example, the first substrate 12 can beplanar, curved, or have both planar and curved portions. In onenon-limiting embodiment, the first substrate 12 can have a thickness inthe range of 0.5 mm to 10 mm, such as 1 mm to 5 mm, such as 2 mm to 4mm, such as 3 mm to 4 mm.

The first substrate 12 can have a high visible light transmission at areference wavelength of 550 nanometers (nm) and a reference thickness of2 mm. By “high visible light transmission” is meant visible lighttransmission at 550 nm of greater than or equal to 85%, such as greaterthan or equal to 87%, such as greater than or equal to 90%, such asgreater than or equal to 91%, such as greater than or equal to 92%, suchas greater than or equal to 93%.

The optional undercoating 18, if present, can be a single layer or amultilayer coating having a first layer and a second layer over thefirst layer. The undercoating 18 can provide a barrier between the firstsubstrate 12 and the overlying coating layers. Silica is known toprovide good barrier properties, particularly as a barrier to sodium iondiffusion out of a glass substrate. Alternatively, the undercoating 18can be a mixture of two or more oxides, such as selected from oxides ofsilicon, titanium, aluminum, tin, zirconium, phosphorous. The oxides canbe present in any desired proportions. The second layer of theundercoating 18, if present, can be a homogeneous coating.Alternatively, the second layer can be a gradient coating with therelative proportions of at least two of the constituents of the coatingvarying through the coating thickness.

The TCO layer 20 comprises at least one conductive oxide layer, such asa doped oxide layer. For example, the TCO layer 20 can include one ormore oxide materials, such as but not limited to, one or more oxides ofone or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co,Cr, Si, In, or an alloy of two or more of these materials, such as zincstannate. The TCO layer 20 can also include one or more dopantmaterials, such as but not limited to, F, In, Al, P, Cu, Mo, Ta, Ti, Ni,Nb, W, and/or Sb.

The TCO layer 20 can have a thickness greater than 200 nm, such asgreater than 250 nm, such as greater than 350 nm, such as greater than380 nm, such as greater than 400 nm, such as greater than 420 nm, suchas greater than 470 nm, such as greater than 500 nm, such as greaterthan 600 nm. For example, The TCO layer can have a thickness in therange of 350 nm to 1,000 nm, such as 400 nm to 800 nm, such as 500 nm to700 nm, such as 600 nm to 700 nm.

The TCO layer 20 can have a surface resistivity (sheet resistance) ofless than 20 ohms per square (Ω/□), such as less than 15Ω/□, such asless than 14Ω/□, such as less than 13.5Ω/□, such as less than 13Ω/□,such as less than 12Ω/□, such as less than 11Ω/□, such as less than10Ω/□.

The TCO layer 20 can have a surface roughness (RMS) in the range of 5 nmto 60 nm, such as 5 nm to 40 nm, such as 5 nm to 30 nm, such as 10 nm to30 nm, such as 10 nm to 20 nm, such as 10 nm to 15 nm, such as 11 nm to15 nm. The surface roughness of the first undercoating layer will beless than the surface roughness of the TCO layer 20.

In a preferred embodiment, the TCO layer 20 is a fluorine doped tinoxide coating, with the fluorine present in an amount less than 20 wt. %based on the total weight of the coating, such as less than 15 wt. %,such as less than 13 wt. %, such as less than 10 wt. %, such as lessthan 5 wt. %, such as less than 4 wt. %, such as less than 2 wt. %, suchas less than 1 wt. %. The TCO layer 20 can be amorphous, crystalline, orat least partly crystalline. However, unlike prior TCO layers, the TCOlayer of the invention does not necessarily have a uniform dopingprofile throughout the coating thickness. In the practice of theinvention, the dopant content can be selected or varied in selectedregions of the TCO layer by the TCO layer formation process describedbelow.

In one preferred embodiment, the TCO layer 20 comprises fluorine dopedtin oxide and has a thickness in the range of 350 nm to 1,000 nm, suchas 400 nm to 800 nm, such as 500 nm to 700 nm, such as 600 nm to 700 nm,such as 650 nm.

The semiconductor layer 22 can be any conventional solar cellsemiconductor material, such as crystalline silicon. Examples includemonocrystalline silicon, polycrystalline silicon, and amorphous silicon.Other examples of semiconductor material include cadmium telluride andcopper indium celenide/sulfide. In a typical silicon solar cell, a layerof phosphorous-doped (n-type) silicon is on top of a thicker boron-doped(p-type) silicon. An electrical field is created at the small p-njunction resulting in a flow of current when the cell is connected to anelectrical load. An amorphous silicon layer 22 can have a thickness inthe range of 200 nm to 1,000 nm, such as 200 nm to 800 nm, such as 300nm to 500 nm, such as 300 nm to 400 nm, such as 350 nm.

The second conductive layer 24 can be a metallic layer or a metalcontaining layer and can include one or more metal oxide materials.Examples of suitable metal oxide materials include, but are not limitedto, oxides of one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn,Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials,such as zinc stannate. The metal containing layer 24 can have athickness in the range of 50 nm to 500 nm, such as 50 nm to 300 nm, suchas 50 nm to 200 nm, such as 100 nm to 200 nm, such as 150 nm.

The optional second substrate 26, if present, can be of any materialdescribed above for the first substrate 12. The first substrate 12 andsecond substrate 26 can be of the same or different material and can beof the same or different thickness.

The undercoating 18, TCO layer 20, semiconductor layer 22, and thesecond conductive layer 24 can be formed over at least a portion of thesubstrate 12 by any conventional method, such as but not limited to,spray pyrolysis, chemical vapor deposition (CVD), or magnetron sputteredvacuum deposition (MSVD). The layers can all be formed by the samemethod or different layers can be formed by different methods. Forexample, the optional undercoating layer 18 and TCO layer 20 can beformed by a CVD method. In a CVD method, a precursor composition iscarried in a carrier gas, e.g., nitrogen gas, and is directed toward theheated substrate. In one practice of the invention, the TCO layer 20 isformed by a CVD coating system in a molten tin bath as described below.

Selective Deposition of TCO Layer

In one preferred practice of the invention and illustrated in FIG. 2,the TCO layer 20 is deposited using a CVD coating system 50 positionedin a molten metal (tin) tin bath 52 of a conventional float glassprocess. The CVD coating system 50 can have one coater or a plurality ofcoaters. In the embodiment shown in FIG. 2, the coating system has afirst CVD coater 54 and a second CVD coater 54. However, any desirednumber of coaters could be used. Each coater 52 and 54 has a pluralityof coating cells (e.g., coating slots) to supply coating material ontoan underlying glass substrate 56 as the glass substrate 56 moves alongon top of the molten metal in the molten metal bath. The generalstructure and operation of a CVD coater and a conventional float glassprocess will, be well understood by one of ordinary skill in the artand, therefore, will not be described in detail.

In the illustrated embodiment, the first coater 52 has three coatingcells A1-A3 and the second coater 54 has seven coating cells B1-B7. Thiscell numbering is arbitrary and is presented simply to aid in discussionof the process described below. Each coating cell can be connected to amanifold to supply a coating composition to the glass. Alternatively,one or more of the cells or a set of the cells can be individuallyconnected to a supply of a coating precursor material and/or a supply ofa dopant precursor material. These connections can be via pipes,conduits, or any other conventional methods. In FIG. 2, the coatingcells B1-B7 of the second coater 54 are each individually connected to arespective coating precursor supply 60 and a dopant precursor supply 62.The first coater 52 can also be configured in similar manner. In onepractice of the invention, the first coater 52 can be used to apply anundercoating on the glass and the second coater 54 can be used to supplya top coat, e.g. TCO coating having a selected dopant profile, asdescribed below. While in the preferred embodiment illustrated in FIG. 2each of the coating cells is individually connected to a coatingprecursor supply 60 and a dopant precursor supply 62, it is to beunderstood that two or more of the cells could be connected to the samecoating precursor supply 60, such as by a manifold, if desirable for aparticular coating configuration. Further, if desired, a dopantprecursor supply 62 could be operatively connected to two or more of thecoating precursor supply 60 conduits, if acceptable for the desiredfinal coating composition.

The coating precursor supplies 60 are a source or container containingthe precursor materials that, when directed onto the hot glass 56, reactor break down to form a coating of a desired composition. To form anoxide coating, the coating precursor material can include materialsthat, when directed onto the hot glass 56, react or combine with oxygento form an oxide. Examples of materials include precursors for oxides ofone or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co,Cr, Si, In, or an alloy of two or more of these materials, such as zincstannate. Such precursor materials are commercially available and can beselected based on a desired coating composition. For example,monobutyltin trichloride (MBTC) is a precursor for tin oxide coatings,tetraethylorthosilicate (TEOS) is a precursor for silica coatings,triisobutylaluminum (TIBAL) is a precursor for alumina coatings.

The dopant precursor supplies 62 are a source or container containing amaterial or dopant to be mixed with the coating precursor material priorto deposition of the coating material onto the glass surface. Commondopant materials include F, In, Al, P, Cu, Mo, Ta, Ti, Ni, Nb, W, and/orSb. For example, tungsten hexafluoride is a precursor for tungsten,trifluoroacetic acid (TFA) is a precursor for fluorine. Such precursormaterials are commercially available and can be selected based on adesired dopant.

The coating composition supplied onto the glass 56 can be varied at eachcoating cell by selecting or varying the amount or the ratio of thecoating precursor material and the dopant precursor material supplied tothe individual cells of the coater from the various coating supplies.For example and for purposes of illustration, each cell can be connectedto a supply of a tin oxide precursor material (such as MBTC) as thecoating precursor supply 60 and a fluorine precursor material (such asTFA) as the dopant precursor supply 62. As will be appreciated, thecells can also be connected to other supplies typical for a CVD coatingprocess, such as a carrier gas supply (such as nitrogen or oxygen) and awater source supply, etc. However, for ease of discussion, these othersources are not specifically shown. By varying the ratio of the coatingcomponents (e.g., coating precursor and dopant precursor) at each cell,the dopant concentration through the resultant coating can be controlledas desired for a particular purpose.

For example, for conventional solar cells, it is desirable that theouter surface of the TCO layer is conductive (i.e., has a low sheetresistance). In prior methods, this was achieved by adding a conductivedopant to a coating precursor material to form a coating composition andthen applying the coating composition onto the glass surface. Theresultant coating had the dopant uniformly distributed throughout thecoating. While this coating did have a conductive outer surface, thedopant located away from the outer surface deeper in the coatingcontributed little to the surface conductivity of the coating andactually was a detriment to the overall coating transparency. In thepresent invention, the dopant concentration can be skewed or selectivelylimited to the outer part (upper portion) of the TCO coating to providea desired sheet resistance but not be present in the depth of thecoating to adversely impact upon the transmission of the layer.

Alternatively, if it is desired that the outer surface of the tin oxidecoating have a high sheet resistance but that the coating be conductive,the dopant material can be preferentially added to be near the bottom ofthe coating and not present near the top of the layer.

Or, should it be desired to have several regions of the coating withmore dopant material than other regions, this also can be achieved byselective addition of the dopant material to selected cells of the CVDcoater(s).

While in the above preferred embodiment individual coating precursorsupplies 60 and dopant precursor supplies 62 were in flow communicationwith the coating cells, it is also possible that individual coatingcells are each connected to a single coating source having a mixture ofa coating precursor material and a dopant precursor material, with theratio of these components being different between the different coatingsources connected to different coating cells.

The following Examples are provided to illustrate various non-limitingaspects of the invention. However, it is to be understood that theinvention is not limited to these specific Examples.

EXAMPLES

The following examples illustrate a fluorine doped tin oxide coatingformed using a tin oxide coating precursor material (MBTC) and afluorine dopant precursor material (TFA). However, it is to beunderstood that this is just to illustrate the general concepts of theinvention and the invention is not limited to these specific materials.

Each of the following examples used clear glass substrates having athickness of 3.2 mm. The TCO coating was deposited by a second coater 54as described above to have a thickness of 665 nm. Cells B1-B7 were used.Each cell had a tin precursor (MBTC) flow rate of 52.3 pounds per hour(lb/hr) and a water flow rate of 14.6 lb/hr. The amount of fluorineprecursor (TFA) for each cell was varied as described in each Example.In the examples, the glass movement was from left to right in FIG. 2.That is, cell B7 was the first active cell of the second coater 54encountered by the glass 56 and cell B1 was the last cell encountered bythe glass. After the coating was formed, the coating was sputter probedusing x-ray photoemission spectrometry to determine the change influorine concentration versus coating depth. The sputter time is anindication of depth, with one second of sputter time equal to about 1.5Angstroms.

Example 1

TFA was supplied to each cell as set forth in FIG. 3. This example useda uniform TFA flow rate to each cell. The coating was sputter probed andthe results shown in FIG. 4. As can be seen from FIG. 4, the fluorineconcentration was relatively uniform through the coating depth. The TCOcoating had a sheet resistance of 8.6Ω/□, a light transmittance of 82.6percent, and a haze of 0.96 percent.

Example 2

TFA was supplied to each cell as set forth in FIG. 5. This example useda lower initial TFA flow rate. The coating was sputter probed and theresults shown in FIG. 6. As can be seen, the fluorine concentration waslower at the bottom of the coating and higher at the top of the coating.The TCO coating had a sheet resistance of 8.8Ω/□, a light transmittanceof 82.8 percent, and a haze of 0.79 percent.

Example 3

TFA was supplied to each cell as set forth in FIG. 7. This example useda higher initial TFA flow rate and a lower final flow rate. The coatingwas sputter probed and the results shown in FIG. 8. As can be seen, thefluorine concentration was higher at the bottom of the coating and lowerat the top of the coating. The TCO coating had a sheet resistance of9.4Ω/□, a light transmittance of 82.1 percent, and a haze of 1.09percent.

Example 4

TFA was supplied to each cell as set forth in FIG. 9. This example useda low initial TFA flow rate, an intermediate flow rate, and then a highflow rate. The coating was sputter probed and the results shown in FIG.10. As can be seen, the fluorine concentration was lower at the bottomof the coating and higher at the top of the coating and had a transitionzone near the middle of the coating. The TCO coating had a sheetresistance of 9.0Ω/□, a light transmittance of 82.7 percent, and a hazeof 0.80 percent.

Example 5

This example shows a TCO coating with discrete step changes in fluorinecomposition as a function of coating depth. The substrate was 3.2 mmclear glass and the coating had a thickness of 385 nm. Six coater cellswere used. The MBTC flow rate was 43.6 lb/hr and the water flow rate was7.9 lb/hr. The TFA flow rate was 8.2 lb/hr in cell 5, 14.03 lb/hr incells 1 and 3, and 0 lb/hr in cells 2, 4, and 6. The coating had thecomposition profile shown in FIG. 11. FIG. 12 shows the F/Sn ratioversus depth for the coating. Discrete areas of fluorine compositionwere formed in the coating. The TCO coating had a sheet resistance of21.0Ω/□, a light transmittance of 84.1 percent, and a haze of 0.70percent.

Example 6

This example illustrates a TCO having a step change in fluorinecomposition as a function of depth to enable the control of haze whilemaintaining a constant sheet resistance. The glass was a low-iron glasshaving a thickness of 4.0 mm. Eight coating cells were used. Cell A3 ofthe first coater is designated “cell 8” in this example and cells 1-7refer to cells B1-B7 described above. Each cell had an MBTC, Water, andTFA flow rate as shown in Table 1. All values are in lbs/hr.

TABLE 1 Cell 8 Cells 7-5 Cells 4-1 Sample # MBTC Water TFA MBTC WaterTFA MBTC Water TFA 1 12.4 2.85 0 28 6.1 0 49.0 11.3 1.8 2 12.4 2.85 0 439.7 0 55.0 12.7 1.4 3 12.4 2.85 0 64 14.4 0 63.0 14.4 1.5

The coatings had the haze and sheet resistance values shown in Table 2.Thickness values are in nm, haze is in percent, and sheet resistance isin ohms per square.

TABLE 2 Sample Total Undoped Doped Sheet # Thickness Thickness ThicknessHaze Resistance 1 900 350 550 7.6 9.9 2 1175 575 600 13.2 10.7 3 1310710 600 16.8 9.9

FIG. 13 is a graph showing the oxygen, tin, and fluorine versus depthfor Sample 1. FIG. 14 is a graph showing the oxygen, tin and fluorinecontent versus depth for Sample 2. FIG. 15 is a graph showing oxygen,tin, and fluorine content versus depth for Sample 3.

FIG. 16 shows the total layer thickness versus haze for Samples 1-3. Ascan be seen, as the thickness increases, the haze increases. FIG. 17shows coating thickness versus sheet resistance for Samples 1-3. As canbe seen, the sheet resistance remained relatively constant even as thecoating thickness increased. FIG. 18 is a graph of transmitted hazeversus wavelength for Samples 1-3.

It will be readily appreciated by those skilled in the art thatmodifications may be made to the invention without departing from theconcepts disclosed in the foregoing description. Accordingly, theparticular embodiments described in detail herein are illustrative onlyand are not limiting to the scope of the invention, which is to be giventhe full breadth of the appended claims and any and all equivalentsthereof.

The invention claimed is:
 1. A method of making a coated substrate having a coating layer with a dopant selectively distributed in the coating layer, comprising the steps of: supplying a coating precursor material to coating cells of a multi-cell chemical vapor deposition coater; supplying a dopant precursor material to coating cells of a multi-cell chemical vapor deposition coater; controlling the supply of at least one of the coating precursor material and the dopant precursor material to define a coating composition having a selected ratio of the dopant precursor material to the coating precursor material at the coating cells; and depositing the coating composition onto a substrate to form a doped coating layer, wherein the ratio of the dopant precursor material to the coating precursor material is selected to define a desired dopant content versus coating depth profile of a resultant doped coating.
 2. The method of claim 1, wherein at least a portion of the coating cells are individually connected to a coating precursor supply and a dopant precursor supply.
 3. The method of claim 1, wherein the coating layer is a transparent conductive oxide layer.
 4. The method of claim 1, wherein the coating precursor material comprises a precursor material for an oxide coating comprising one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials.
 5. The method of claim 1, wherein the dopant precursor material comprises at least one dopant selected from F, In, Al, P, and Sb.
 6. The method of claim 1, including controlling the supply of at least one of the coating precursor material and the dopant precursor material such that the dopant is non-uniformly distributed within the tin oxide layer.
 7. The method of claim 1, wherein the coating precursor material comprises a tin oxide precursor to form a tin oxide layer and the dopant precursor material comprises a fluorine precursor.
 8. The method of claim 7, wherein a fluorine content is higher at a top of the tin oxide layer than near a bottom of the tin oxide layer.
 9. The method of claim 7, wherein a fluorine content is lower at a top of the tin oxide layer than near a bottom of the tin oxide layer.
 10. The method of claim 7, wherein a fluorine content is higher in a middle region of the tin oxide layer than at a top or bottom of the tin oxide layer.
 11. A solar cell, comprising: a first substrate having a first surface and a second surface; a first conductive layer over at least a portion of the second surface, wherein the first conductive layer is a transparent conductive oxide layer incorporating a dopant material, wherein the dopant material is selectively distributed in the conductive layer; a semiconductor layer over the transparent first conductive layer; and a second conductive layer over at least a portion of the semiconductor layer.
 12. The solar cell of claim 11, further comprising an undercoating layer between the second surface and the first conductive layer.
 13. The solar cell of claim 11, further comprising a second substrate over the second conductive layer.
 14. The solar cell of claim 11, wherein the first conductive layer comprises oxides of one or more of Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In, or an alloy of two or more of these materials.
 15. The solar cell of claim 14, wherein the first conductive layer comprises at least one dopant selected from F, In, Al, P, and Sb.
 16. The solar cell of claim 15, wherein the first conductive layer comprises fluorine-doped tin oxide layer.
 17. The solar cell of claim 16, wherein the fluorine is non-uniformly distributed within the tin oxide layer.
 18. The solar cell of claim 17, wherein a fluorine content is higher at a top of the tin oxide layer than near a bottom of the tin oxide layer.
 19. The solar cell of claim 1, wherein the semiconductor layer is selected from monocrystalline silicon, polycrystalline silicon, amorphous silicon, cadmium telluride, and copper indium celenide/sulfide.
 20. A chemical vapor deposition system, comprising: at least one coater having a plurality of coating cells, wherein the coating cells are individually connected to respective coating supply sources comprising at least one oxide precursor material and at least one dopant material. 